Ether amines for enhanced sporicidal performance

ABSTRACT

A composition and method are used to treat articles suspected of contamination with bacterial spores. The composition and method are effective against bacterial spores selected from  C. diff., C. botulinum, C. sporogenes, B. cereus , and  B. subtilis . The article can be a textile or a hard surface. The method includes preparing a first use solution by mixing ether amine in water and a second use solution by mixing percarboxylic acid in water; applying the first use solution to the article; and applying the second use solution to the article. An alternative method includes preparing a mixture of ether amine, percarboxylic acid, and water, and applying the mixture to the article.

CROSS REFERENCE TO RELATED APPLICATIONS

This application claims the benefit of U.S. Provisional Application No.62/299,616, filed on Feb. 25, 2016, which application is herebyincorporated by reference in its entirety.

FIELD

The present disclosure relates to a composition and method for providinga sporicidal effect. In particular, the present disclosure relates tocompositions comprising one or more ether amines and their derivativesand one or more peracids, and methods for preparation and use of suchcompositions.

BACKGROUND

Control of bacteria and their spores is desirable in industrial andinstitutional settings, including industrial and institutional cleaningand laundry applications. For example, it is desirable to reduce oreliminate bacterial spores, such as spores of Clostridium difficile (“C.diff”), Clostridium botulinum (“C. botulinum”), Clostridium sporogenes(“C. sporogenes”), Bacillus cereus (“B. cereus”), and Bacillus subtilis(“B. subtilis”) from surfaces, instruments, and from industrial andinstitutional laundry (e.g., health care facilities) to minimize theoccurrence of diseases, such as gut infections cause by C. diff or B.cereus.

Standard oxidative chemistries, such as chlorine (e.g., hypochlorite)and peracids can be effective against C. diff spores, but typicallyrequire high concentrations of chemicals. Current CDC guidelinesrecommend hypochlorite concentrations between 1,000-5,000 ppm fordisinfection of C. diff spores on hard surfaces. However, thisconcentration is at least an order of magnitude higher than the typicalhypochlorite dose of 100 ppm for laundry sanitizing.

It would be beneficial to provide for a cost-effective, yet efficient,method for sanitizing and/or disinfecting laundry (soft surfaces) andhard surfaces. In particular, it would be beneficial to provide for anefficient and cost-effective composition and method for reducing oreliminating bacterial spores, including C. diff, in laundry and on hardsurfaces. It would further be beneficial to provide for a compositionhaving sporicidal activity and improved water solubility; to provide fora composition having sporicidal activity and improved stability in thepresence of water hardness; and to provide for a method for eradicatingspores by a composition with improved water solubility and stability.

SUMMARY

A composition and method are used to treat articles suspected ofcontamination with bacterial spores. The composition and method areeffective against bacterial spores selected from C. diff., C. botulinum,C. sporogenes, B. cereus, and B. subtilis. The article can be a textileor a hard surface. The method includes preparing a first use solution bymixing ether amine in water and a second use solution by mixingpercarboxylic acid in water; applying the first use solution to thearticle; and applying the second use solution to the article. Analternative method includes preparing a mixture of ether amine,percarboxylic acid, and water, and applying the mixture to the article.

BRIEF DESCRIPTION OF DRAWINGS

FIG. 1 is a two-chamber spray bottle used to house and apply thecomposition according to an embodiment.

DETAILED DESCRIPTION

The present disclosure relates to methods of treating laundry or varioussurfaces to reduce bacterial spores. The present disclosure furtherrelates to compositions with sporicidal activity that exhibit improvedsolubility and stability in water.

As used in this invention, the term “sporicide” refers to a physical orchemical agent or process having the ability to cause greater than a 90%reduction (1-log order reduction) in the population of spores ofBacillus subtilis, Clostridium difficile, or Clostridium sporogeneswithin 30 min at room temperature.

According to some embodiments, the compositions and methods of thepresent disclosure are effective against spores of one or more of C.diff., C. botulinum, C. sporogenes, B. cereus, and B. subtilis. In atleast one embodiment, compositions and methods are effective againstspores of C. diff, C. botulinum, C. sporogenes, B. cereus, and B.subtilis. For example, embodiments of the present compositions haveadvantageous sporicidal activity against C. diff and otherdifficult-to-kill bacterial endospores, such as those of C. sporogenesand B. subtilis. Further, the present compositions are also activeagainst vegetative bacteria, vegetative fungi, other bacterial spores,fungal spores, and viruses.

In certain embodiments, the sporicidal compositions provide greater thana 99% reduction (2-log order reduction), greater than a 99.9% reduction(3-log order reduction), greater than a 99.99% reduction (4-log orderreduction), or greater than a 99.999% reduction (5-log order reduction)in populations of spores, or total inactivation of endospores within 30min at room temperature. In an embodiment, the present sporicidalcomposition eliminates all bacterial endospores within the stated timeand temperature, e.g., 30 min at room temperature. To test sporicidalefficiency, a test strip comprising bacterial spores can be used.Standard test methods for evaluating efficiency of the composition andmethod can be used, such as ASTM method E2274, as specified by the U.S.Environmental Protection Agency (EPA) Product Performance TestGuidelines, document OCSPP 810.2400. ASTM E2274 requires that the teststrips be inoculated in a bacteria solution containing at least 10⁸colony forming units (CFU) per mL. For the test to be valid, a minimumaverage of 1.0×10⁴ CFU/carrier and 1.0×10⁴ CFU/mL in the wash watershould be recovered after the test from the control system.

The method and composition of the present disclosure can be used totreat a variety of surfaces, substances, and articles for which it isdesirable to reduce microbial contamination, particularly microbialcontamination arising from spores of microorganisms. Examples of suchsubstances and articles include textiles (e.g., cottons, wools, silks,rayon, viscose, and synthetic fabrics such as polyesters, polyolefins,and acrylics, blends of fibers such as cotton-polyester blends, etc.),wood and cellulose-based systems (e.g., paper), food handling surfaces(e.g., countertops, food handling equipment and packaging, utensils),general premise surfaces (e.g., floors, walls, ceilings, exterior offurniture, etc.), or equipment surfaces (e.g., medical equipment,manufacturing equipment, processing equipment, etc.).

According to some embodiments, the compositions and methods of thepresent disclosure are more cost-effective than treatments usinghypochlorite and/or peracids at concentrations that achieve the samelevel of efficiency.

According to at least some embodiments, the composition of the presentdisclosure comprises one or more ether amines, one or more peracids, andoptionally other antimicrobial agents and detersive components, such assurfactants. The composition may also include additional components,such as solvents, salts, pH modifiers, fillers, coloring agents,fragrances, etc.

Use of dodecylamine has been found to be beneficial against sporegermination of pathogenic bacteria, such as C. diff. However, inclusionof dodecylamine in an aqueous composition, such as a detergentcomposition, has been problematic because of the limited solubility oflong chain amines particularly in the presence of water hardness. It hasbeen discovered that ether amines in combination with peroxyacids show asynergistic sporicidal effect against bacterial spores, such as those ofC. diff. It has further been discovered that ether amines exhibit goodsolubility and stability in water. A comparison of calculatedsolubilities for dodecylamine (CAS 124-22-1; a traditional amine) and3-octyloxy-1-propanamine (CAS (15930-66-2; ether amine with the samechain length as dodecylamine) is shown in the table below.

TABLE 1 Solubility Solubility g/L at 25° C. pH Dodecylamine1-Propanamine, 3-(octyloxy)- 6 150 1000 7 120 847 8 43 120 9 5.7 14 100.7 3.4 Calculated using Advanced Chemistry Development (ACD/Labs)Software V11.02

According to some embodiments, the composition is prepared from twoparts, part I and part II, which can be applied consecutively,cumulatively, or simultaneously. When parts I and II are appliedconsecutively, an article can be treated first with part I and then withpart II. When parts I and II are applied cumulatively, part I can firstbe applied to the article and then part II, without first removing partI. The parts may also be applied in reverse order, first applying partII and then part I, without first removing part II. In an embodiment,where the composition is used to treat laundry, the parts I and II canbe applied directly to the wash solution to create the composition.Parts I and II can be applied to the wash solution consecutively,cumulatively or simultaneously. In another embodiment, where thecomposition is used to treat a surface (e.g., a hard surface), parts Iand II can be applied directly to the surface (either consecutively,cumulatively or simultaneously), or can be first diluted and thenapplied to the surface, or can be mixed to produce a mixture of parts Iand II that can then be applied to the surface.

The term “composition” is used here to refer to the use solution thatmay be a two-part solution with parts I and II, or a mixture comprisingparts I and II. The designations “part I” and “part II” used here arearbitrary and should not be considered limiting.

Amines

In an embodiment, the present composition can include an effectiveamount (e.g., sporicidal amount) of ether amine. The ether amine can beprovided as part I of the composition, or may be provided as part of amixture of parts I and II.

Suitable ether amines include primary, secondary, or tertiary etheramines. Ether amines generally have the following formula:N(R^(a))(R^(b))(R^(c)), where at least one of R^(a), R^(b), and R^(c)includes an ether moiety. For example, the ether amine can be:

a primary ether amine of Formula 1: R¹OR²NH₂;

a secondary ether amine of Formula 2: (R¹OR²)(R³OR⁴)NH or Formula 3:(R¹OR²)R³NH;

a tertiary ether amine of Formula 4: (R¹OR²)(R³OR⁴)N(R⁵OR⁶), Formula 5:(R¹OR²)(R³OR⁴)NR⁵, or Formula 6: (R¹OR²)R³NR⁵;

a diamine of Formula 7: R¹OR²NHR³NH₂; or

a mixture thereof.

In suitable ether amines, R₁, R₂, R₃, R₄, R₅, and R₆ may beindependently selected from C1-C22 alkyl groups. In preferredembodiments, R₁ comprises a relatively longer carbon chain, whereasR₂-R₆ comprise shorter carbon chains. The alkyl groups may be saturatedor unsaturated, aliphatic or cyclic, unsubstituted or substituted,linear or branched. The ether amine may be in salt form, such as anether ammonium salt. In an embodiment, the composition comprises one ormore diamines.

Examples of suitable ether amines include alkyloxyalkylamines, such ashexyloxypropylamine, tetradecyloxypropyl-1,3-propylamine, anddodecyloxypropyl-1,3-propylamine; branched alkyloxyalkylamines, such asethylhexyloxypropylamine, isotridecyloxypropylamine, andisodecyloxypropylamine; or alkyloxydiamines, such asoctyloxypropyl-1,3-propylenediamine,decyloxypropyl-1,3-propylenediamine,isodecyloxypropyl-1,3-propylenediamine,dodecyloxypropyl-1,3-propylenediamine,tetradecyloxypropyl-1,3-propylenediamine, orisotridecyloxypropyl-1,3-propylenediamine.

Ether amines are commercially available, for example, from Air Productsand Chemicals, Inc. in Allentown, Pa.; Clariant Corp. in Charlotte,N.C.; and BASF Corporation in Florham Park, N.J. Available productsinclude, for example, Air Products' TOMAMINE® PA-19, PA-1618, PA-1816,DA-18, DA-19, DA-1618, and DA-1816. In an embodiment, the compositioncomprises PA-14, DA-1214, DA-1618, or a combination thereof.

Peracids

According to at least one embodiment, the composition comprises one ormore peroxycarboxylic acids (also known as peracids) or salts thereof,or hydrogen peroxide. In some embodiments, the composition comprises anaqueous equilibrium of carboxylic acid and correspondingperoxycarboxylic acid. Such an equilibrium also typically includes anequilibrium amount of hydrogen peroxide. For example, the compositionmay comprise acetic acid, peroxyacetic acid, and hydrogen peroxide inequilibrium. The peroxycarboxylic acid can also be provided as aprecursor (e.g., an ester precursor) that can be converted toperoxycarboxylic acid (e.g., by reacting the ester precursor withhydrogen peroxide). The peroxycarboxylic acid or hydrogen peroxide canbe provided as part II of the composition, or may be provided as part ofa mixture of parts I and II.

Peroxycarboxylic (or percarboxylic) acids generally have the formulaR(CO₃H)_(n), where, for example, R is an alkyl, arylalkyl, cycloalkyl,aromatic, or heterocyclic group, and n is one, two, or three. TheR-group can be saturated or unsaturated as well as substituted orunsubstituted. Peroxycarboxylic acids are typically named by prefixingthe parent acid with peroxy.

The composition and methods of the invention can employ short and/ormedium chain peroxycarboxylic acids containing, for example, from 2 to11, from 2 to 7, or from 2 to 5 carbon atoms. For example, medium chainperoxycarboxylic (or percarboxylic) acids can have the formulaR(CO₃H)_(n), where R is a C₁-C₆ alkyl group, a C₃-C₁₁ cycloalkyl, aC₅-C₁₁ arylalkyl group, C₅-C₁₁ (e.g., C₆) aryl group, or a C₅-C₁₁heterocyclic group; and n is one, two, or three. Peroxyacetic (orperacetic) acid is a peroxycarboxylic acid having the formula CH₂COOOH.Peroxyhexanoic (or perhexanoic) acid is a peroxycarboxylic acid havingthe formula, for example, of n-peroxyhexanoic acid: CH₃(CH₂)₄COOOH. Thecarbon chain of the peroxycarboxylic acid can be a straight chain alkylmoiety, an acid with a branched alkyl moiety, or a mixture thereof.

Suitable peroxycarboxylic acids include short chain peroxycarboxylicacids and medium chain peroxycarboxylic acids and mixtures therefor. Forexample, suitable peroxycarboxylic acids include peroxyacetic,peroxybutanoic, peroxypropanoic, peroxypentanoic, peroxyhexanoic,peroxyheptanoic, peroxyoctanoic, peroxysalicylic, and peroxybenzoicacids. In certain embodiments, the peroxycarboxylic acid comprisesperoxyacetic acid, peroxybutanoic acid, peroxypropanoic acid,peroxypentanoic acid, peroxyhexanoic acid, peroxyoctanoic, or a mixturethereof. In an embodiment, the peroxycarboxylic acid includes or isperoxyacetic acid.

In some embodiments it may be desirable to choose the peroxycarboxylicacid with a short chain length that is not hydrophobic. For example, theperoxycarboxylic acid may have a chain length of 4 carbons or less.Particularly if the peroxycarboxylic acid is added to a solutiontogether with the ether amine, hydrophobicity caused by a longer chainlength may cause the peroxycarboxylic acid and ether amine toagglomerate, thus reducing the efficacy of the solution.

According to some embodiments, the composition comprises one or morecarboxylic acids. Carboxylic acids can have one, two, three, or morecarboxyl groups. The composition and methods of the invention typicallyemploy short and/or medium chain carboxylic acids containing, forexample, from 2 to 12, from 2 to 9, or from 2 to 5 carbon atoms. Forexample, medium chain carboxylic acids can have the formula R—COOH inwhich R can be a C₁-C₁₁ alkyl group, a C₃-C₁₁ cycloalkyl group, a C₅-C₁₁arylalkyl group, C₅-C₁₁ (e.g., C₆) aryl group, or a C₅-C₁₁ heterocyclicgroup. Suitable carboxylic acids include acetic acid, butanoic acid,propanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoicacid, salicylic acid, benzoic acid, mixtures thereof, or the like. Thealkyl backbones of the medium chain carboxylic acids can be straightchain, branched, or a mixture thereof.

According to embodiments, the composition comprises an effective amountof ether amines and peroxygen compounds (e.g., peracids), applied eitherseparately as parts I and II, or as a mixture of parts I and II. Thecomposition may comprise about 10 to 2,000 ppm, about 20 to 1,500 ppm,about 25 to 1,000 ppm, about 30 to 800 ppm, about 40 to 600 ppm, about50 to 500 pm, or about 100 to 5,000 ppm of ether amines. For example,the composition may comprise about 10 ppm, about 20 ppm, about 30 ppm,about 40 ppm, about 50 ppm, about 75 ppm, about 100 ppm, about 125 ppm,about 150 ppm, about 200 ppm, about 250 ppm, about 300 ppm, about 400ppm, about 500 ppm, about 750 ppm, about 1,000 ppm, about 1,250 ppm, orabout 1,500 ppm ether amines, or any amount therebetween. If the etheramine comprises two or more different ether amines, the ether amines maybe present at any ratio relative to one another. In an exemplaryembodiment, the ether amines are provided in part I of the composition.

The composition may comprise about 10 to 10,000 ppm, or about 20 to8,000 ppm, or about 50 to 6,000 ppm, about 50 to 3,000 ppm, about 50 to1,500 ppm, about 50 to 1,000 ppm, about 20 to 500 pm, or about 50 to5,000 ppm of peracids. For example, the composition may comprise about10 ppm, about 20 ppm, about 30 ppm, about 40 ppm, about 50 ppm, about 75ppm, about 100 ppm, about 125 ppm, about 150 ppm, about 200 ppm, about250 ppm, about 300 ppm, about 400 ppm, about 500 ppm, about 750 ppm,about 1,000 ppm, about 1,250 ppm, about 1,500 ppm, about 2,000 ppm,about 2,500 ppm, about 3,000 ppm, about 4,000 ppm, about 5,000 ppm,about 7,500 ppm, or about 10,000 ppm peracids, or any amounttherebetween. If the peracid comprises two or more different peracids,the peracids may be present at any ratio relative to one another.

Exemplary embodiments of the composition are shown in TABLE 2 below. Theether amines and peracids may be provided in separate parts of thecomposition, e.g., part I and part II, respectively, or as a mixture ofparts I and II.

TABLE 2 Ether amine and peracid concentrations. Ether Amines Peracids(ppm) (ppm) Composition A 15-200 50-500 Composition B 15-200 500-1000Composition C 50-300 100-500  Composition D 50-300 500-1200 CompositionE 250-500  100-500  Composition F 250-500  500-1500 Composition G500-1000 500-1000 Composition H 500-1000 1000-2000 

In a preferred embodiment, the composition comprises about 2500 ppm orless of ether amines and about 1000 ppm or less of peracids. In anotherpreferred embodiment, the composition comprises about 50 to 1000 ppm ofether amines, and about 200 to 750 ppm of peracids.

In an embodiment, the composition comprises a two-part composition withpart I and part II. Parts I and II can be provided as concentrates thatmay be diluted with a solvent prior to use. For example, parts I and IImay be concentrated solutions of ether amines and peracids(respectively) that are added to a use solution (e.g., a wash solutionto wash laundry, or to a spray to be applied to textiles or surfaces) ina suitable amount to create a sporicidal effect. The composition (or itsparts) may be provided as a concentrate that may be diluted about 1:1,about 1:5, about 1:10, about 1:100, about 1:100-1:1,000, about1:500-1:2,000, about 1:1,000-1:10,000, about 1:5,000-1:100,000, or about1:1,000-1:100,000 to prepare a use solution. The part I concentratesolution may comprise ether amines at about 95 to 100 wt-% (when etheramine is provided “neat,” without significant dilution), or at about 1to about 25 wt-%, about 5 to about 20 wt-%, or about 5 to about 10 wt-%.The part II concentrate solution may comprise peracids at about 1 toabout 35 wt-%, about 2 to about 25 wt-%, about 4 to about 20 wt-%, orabout 5 to about 15 wt-%. Alternatively the peracid may be prepared bymixing the corresponding carboxylic acid with hydrogen peroxide andallowing the mixture to equilibrate, or may be prepared from aprecursor, such as a suitable ester. The ether amines may comprise oneor more different ether amines. Similarly, the peracids may comprise oneor more different peracids. Suitable solvents for diluting theconcentrate include water and aqueous solvents, such as aqueous alcoholsor other suitable solvents.

In some embodiments, the composition is a mixture of ether amine,peracid, and water, and optionally one or more additional components.For example, the mixture may contain from about 10 to about 1,500 ppm,from about 20 to about 1,000 ppm, from about 50 to about 500 ppm, orfrom about 75 to about 300 ppm ether amines; and from about 10 to about1,500 ppm, from about 20 to about 1,000 ppm, from about 50 to about 500ppm, or from about 75 to about 300 ppm peracids.

Additional Components

In some embodiments, the composition can be provided as a booster (e.g.,a laundry booster), added to a use or wash solution in addition toanother composition, such as laundry detergent. In other embodiments,the composition is formulated as a complete detergent composition,including for example, suitable surfactants and other components. In yetother embodiments, the composition can comprise two or more parts of amulti-part system, where different parts can be applied or usedsimultaneously or consecutively. Such multi-part system can comprise acomplete detergent composition or be formulated to be mixed with othercomponents to provide a use or wash solution.

The composition may include any number of additional agents oradjuvants. Specifically, the composition may comprise one more of anantimicrobial agent, surfactant, defoaming agent, wetting agent,potentiator (also referred to as a synergist to the active ingredients),thickener, stabilizing agent, hydrotrope or coupling agent, aestheticenhancing agent (e.g., a colorant, odorant, fragrance, or maskingagent), manufacturing processing aid, preserving agent, or tracer. Suchadjuvants can be formulated with the sporicidal composition or added tothe system simultaneously, or after, the addition of the sporicidalcomposition. In some embodiments the composition is formulated for usewith laundering, and the composition can be formulated to comprisenon-irritating components. In some other embodiments the composition isformulated for use with food contact surfaces, and the composition mayinclude food grade components.

The composition may optionally comprise additional antimicrobial agents.Additional antimicrobial agent can be added to use compositions beforeuse. Examples of suitable antimicrobial agents include active oxygencompounds, halogen containing compounds, amine or quaternary ammoniumcompounds, sulfonic acids, phenolic derivatives, or the like. Commonactive oxygen compounds include, for example, hydrogen peroxide,percarbonate, perborate, and the like. Halogen containing antibacterialagents include sodium trichloroisocyanurate, sodium dichloro isocyanate(anhydrous or dihydrate), iodine-poly(vinylpyrolidinone) complexes,bromine compounds such as 2-bromo-2-nitropropane-1,3-diol, andquaternary antimicrobial agents such as benzalkonium chloride,didecyldimethyl ammonium chloride, choline diiodochloride, tetramethylphosphonium tribromide. Amine or quaternary ammonium compounds include,for example, alkyl dimethylbenzyl ammonium chloride, dialkyldimethylammonium chloride, and N-dialkylethylbenzyl ammonium chloride. Asuitable sulfonic acid can be, for example, dodecylbenzene sulfonicacid. Phenolic antimicrobials include pentachlorophenol,orthophenylphenol, a chloro-p-benzylphenol, p-chloro-m-xylenol tert-amylphenol, and C₁-C₆ alkyl hydroxy benzoates. Other antimicrobialcompositions include hexahydro-1,3,5-tris(2-hydroxyethyl)-s-triazine,dithiocarbamates such as sodium dimethyldithiocarbamate, and a varietyof other materials are known in the art for their antimicrobialproperties.

In some embodiments, an antimicrobial component can be included in therange of 0.001 to 25 wt-% of the composition, about 0.01 to 15 wt-%, orabout 0.05 to about 10 wt-%.

The composition may comprise one or more surfactants. Suitablesurfactants include water-soluble or water-dispersible nonionic,anionic, cationic, amphoteric, semi-polar nonionic surfactants, andzwitterionic surface active agents. In some embodiments, the compositioncomprises low-foaming or non-foaming surfactants.

The one or more surfactants can be added in the composition at anysuitable concentration. As with any charged components, care should betaken not to cause any inadvertent negative effects, such as issues withsolubility. The surfactants can be present in a use solution at aconcentration range of about 100 to 7000 ppm, about 250 to 6500 ppm,about 400 to 6000 ppm, about 600 to 5500 ppm, or about 1000 to 5000 ppm.The amount of surfactants in the composition can be adjusted accordingto the intended dilution (if any) and end use. For example, in typicallaundry applications the amount of surfactant in the use solution ismore diluted and may be about 200-1200 ppm, whereas in a typical hardsurface cleaning application the amount of surfactant in the usesolution may be about 1500-5000 ppm.

Nonionic Surfactants

Examples of suitable nonionic surfactants include alkoxylatedsurfactants. Suitable alkoxylated surfactants include alcoholethoxylates, EO/PO copolymers, capped EO/PO copolymers, alcoholalkoxylates, capped alcohol alkoxylates, mixtures thereof, or the like.Suitable alkoxylated surfactants for use as solvents include EO/PO blockcopolymers, such as the Pluronic and reverse Pluronic surfactants;alcohol alkoxylates, such as Dehypon LS-54 (R-(EO)₅(PO)₄) and DehyponLS-36 (R-(EO)₃(PO)₆); and capped alcohol alkoxylates, such as PlurafacLF221 and Tegoten EC11; mixtures thereof, or the like. When employed asa solvent a surfactant, such as a nonionic surfactant, can be atconcentrations higher than those conventionally employed as surfactant.

Cationic Surfactants

Surface active substances are classified as cationic if the charge onthe hydrotrope portion of the molecule is positive. In theory, cationicsurfactants may be synthesized from any combination of elementscontaining an “onium” structure R_(n)X⁺Y⁻— and could include compoundsother than nitrogen (ammonium) such as phosphorus (phosphonium) andsulfur (sulfonium). In practice, the cationic surfactant field isdominated by nitrogen containing compounds. Cationic surfactantspreferably include compounds containing at least one long carbon chainhydrophobic group and at least one positively charged ion.

Examples of suitable cationic surfactants include quaternary ammoniumsalts, e.g., alkylquaternary ammonium chloride surfactants such asalkyldimethylbenzylammonium chloride (ADBAC) or dialklyldimethylammoniumchloride (DADMAC), and n-tetradecyldimethylbenzylammonium chloridemonohydrate, and a naphthylene-substituted quaternary ammonium chloridesuch as dimethyl-1-naphthylmethylammonium chloride; amines such asprimary, secondary and tertiary monoamines with alkyl or alkenyl chains,ethoxylated alkylamines, alkoxylates of ethylenediamine, imidazoles suchas a 1-(2-hydroxyethyl)-2-imidazoline, a2-alkyl-1-(2-hydroxyethyl)-2-imidazoline, and the like.

Anionic Surfactants

Suitable anionic surfactants include sulfonic acids and their salts(sulfonates), phosphate esters, carboxylates, mixtures thereof, and thelike. Persons skilled in the art will recognize the need to avoidcausing unintentional reactions between anionic surfactants and othercharged surfactants, such as ether amines, and would recognize that theamount of anionic surfactants needs to be balanced with the amounts ofsuch other charged surfactants. Preferably, the concentration of anionicsurfactants in the use solution is in the range of 0 ppm to 600 ppm, orabout 10 ppm to 500 ppm, or about 20 ppm to 200 ppm. For example, theuse solution may comprise up to 500 ppm, 400 ppm, 300 ppm, 250 ppm, or200 ppm anionic surfactants.

Anionic sulfate surfactants suitable for use in the present compositionsinclude alkyl ether sulfates, alkyl sulfates, the linear and branchedprimary and secondary alkyl sulfates, alkyl ethoxysulfates, fatty oleylglycerol sulfates, alkyl phenol ethylene oxide ether sulfates, theC₅-C₁₇ acyl-N—(C₁-C₄ alkyl) and —N—(C₁-C₂ hydroxyalkyl) glucaminesulfates, and sulfates of alkylpolysaccharides such as the sulfates ofalkylpolyglucoside, and the like.

Anionic carboxylate surfactants suitable for use in the presentcompositions include carboxylic acids (and salts), such as alkanoicacids (and alkanoates), ester carboxylic acids (e.g. alkyl succinates),ether carboxylic acids, and the like. Such carboxylates include alkylethoxy carboxylates, alkyl aryl ethoxy carboxylates, alkyl polyethoxypolycarboxylate surfactants and soaps (e.g. alkyl carboxyls). Secondarycarboxylates useful in the present compositions include those whichcontain a carboxyl unit connected to a secondary carbon. Suitablecarboxylates also include acylamino acids (and salts), such asacylgluamates, acyl peptides, sarcosinates (e.g. N-acyl sarcosinates),taurates (e.g. N-acyl taurates and fatty acid amides of methyl tauride),and the like.

Semi-Polar Nonionic Surfactants

The composition may further comprise one or more semi-polar nonionicsurfactants. Suitable semi-polar nonionic surfactants include, forexample, phosphine oxides, sulfoxides and their alkoxylated derivatives.

Amphoteric Surfactants

Amphoteric, or ampholytic, surfactants contain both a basic and anacidic hydrophilic group and an organic hydrophobic group. These ionicentities may be similar to the anionic or cationic groups comprised inthe other types of surfactants. Typical functional groups in amphotericsurfactants include a basic nitrogen group and an acidic carboxylategroup. In some amphoteric surfactants the negative charge is provided bya sulfonate, sulfate, phosphonate, or phosphate group.

Amphoteric surfactants can be broadly described as derivatives ofaliphatic secondary and tertiary amines, in which the aliphatic radicalmay be straight chain or branched and wherein one of the aliphaticsubstituents contains from about 8 to 18 carbon atoms and one containsan anionic water solubilizing group, e.g., carboxy, sulfo, sulfato,phosphato, or phosphono. Amphoteric surfactants are subdivided into twomajor classes known to those of skill in the art and described in“Surfactant Encyclopedia” Cosmetics & Toiletries, Vol. 104 (2) 69-71(1989). The first class includes acyl/dialkyl ethylenediaminederivatives (e.g. 2-alkyl hydroxyethyl imidazoline derivatives) andtheir salts. The second class includes N-alkylamino acids and theirsalts. Some amphoteric surfactants can be envisioned as fitting intoboth classes.

Zwitterionic Surfactants

Zwitterionic surfactants can be thought of as a subset of the amphotericsurfactants and can include an anionic charge. Zwitterionic surfactantscan be broadly described as derivatives of secondary and tertiaryamines, derivatives of heterocyclic secondary and tertiary amines, orderivatives of quaternary ammonium, quaternary phosphonium or tertiarysulfonium compounds. Typically, a zwitterionic surfactant includes apositive charged quaternary ammonium or, in some cases, a sulfonium orphosphonium ion; a negative charged carboxyl group; and an alkyl group.Zwitterionics generally contain cationic and anionic groups which ionizeto a nearly equal degree in the isoelectric region of the molecule andwhich can develop strong “inner-salt” attraction betweenpositive-negative charge centers. Examples of such zwitterionicsynthetic surfactants include derivatives of aliphatic quaternaryammonium, phosphonium, and sulfonium compounds, in which the aliphaticradicals can be straight chain or branched, and wherein one of thealiphatic substituents contains from 8 to 18 carbon atoms and onecontains an anionic water solubilizing group, e.g., carboxy, sulfonate,sulfate, phosphate, or phosphonate. Betaine and sultaine surfactants areexemplary zwitterionic surfactants for use herein.

The composition may comprise one or more defoaming agents. Suitabledefoaming agents include, for example, silicones, aliphatic acids oresters; alcohols; sulfates or sulfonates; amines or amides; vegetableoils, waxes; mineral oils as well as their sulfated derivatives; fattyacid soaps such as alkali, alkaline earth metal soaps; and mixturesthereof. Examples of suitable silicone defoaming agents include dimethylsilicone, glycol polysiloxane, methylphenol polysiloxane, trialkyl ortetraalkyl silanes, and hydrophobic silica defoamers. The defoamingagents can be present at a concentration range of about 0.01 wt-% to 5wt-%, about 0.01 wt-% to 2 wt-%, or about 0.01 wt-% to about 1 wt-%.

The composition may comprise one or more wetting agents. Wetting agentsfunction to increase the surface contact or penetration activity of thesporicidal composition.

The composition may comprise one or more thickeners or gelling agents.Suitable thickeners include, for example, inorganic thickeners, organicthickeners, oligomeric thickeners, and associative thickeners. These mayinclude natural gums such as xanthan gum, guar gum, or other gums fromplant mucilage; modified cellulose derivatives; oligomeric organicthickeners; and hydrocolloid thickeners, such as pectin; and inorganicsilicates and clays. In an embodiment, the thickener does not leavecontaminating residue on the surface of an object. The thickeners orgelling agents can be compatible with food or other sensitive productsin contact areas. Generally, the concentration of thickener employed inthe present compositions will be dictated by the desired viscosity ofthe final composition or use solution. However, as a general guideline,the quantity of thickener suitable for use in the present compositionranges from about 0.1 wt-% to about 1.5 wt-%, about 0.1 wt-% to about 1wt %, or about 0.1 wt-% to about 0.5 wt-%.

The composition can optionally be formulated as a solid (e.g., a cast orpressed block, a powder, or a granulated powder) by using asolidification agent. In an exemplary embodiment, the composition isformulated in block form with a detergent. Examples of suitablesolidification agents include solid polyethylene glycol (PEG), solidpolypropylene glycol, solid EO/PO block copolymer, amide, urea (alsoknown as carbamide), nonionic surfactant (which can be employed with acoupler), starch that has been made water-soluble (e.g., through an acidor alkaline treatment process), cellulose that has been madewater-soluble, inorganic agent, poly(maleic anhydride/methyl vinylether), polymethacrylic acid, other generally functional or inertmaterials with high melting points, mixtures thereof, and the like.

Exemplary glycol solidification agents include a solid polyethyleneglycol or a solid polypropylene glycol, which can, for example, havemolecular weight of about 1,400 to about 30,000. In certain embodiments,the solidification agent includes or is solid PEG, for example PEG 1500up to PEG 20,000. In certain embodiments, the PEG includes PEG 1450, PEG3350, PEG 4500, PEG 8000, PEG 20,000, and the like. Suitable solidpolyethylene glycols are commercially available from Union Carbide underthe tradename CARBOWAX.

Exemplary amide solidification agents include stearic monoethanolamide,lauric diethanolamide, stearic diethanolamide, stearic monoethanolamide, cocodiethylene amide, an alkylamide, mixtures thereof, and thelike.

Exemplary nonionic surfactant solidification agents include nonylphenolethoxylate, linear alkyl alcohol ethoxylate, ethylene oxide/propyleneoxide block copolymer, mixtures thereof, or the like. Exemplary ethyleneoxide/propylene oxide block copolymers include those sold under thePluronic tradename (e.g., Pluronic 108 and Pluronic F68) andcommercially available from BASF Corporation. In some embodiments, thenonionic surfactant can be selected to be solid at room temperature orthe temperature at which the composition will be stored or used. Inother embodiments, the nonionic surfactant can be selected to havereduced aqueous solubility in combination with the coupling agent.Suitable couplers that can be employed with the nonionic surfactantsolidification agent include propylene glycol, polyethylene glycol,mixtures thereof, or the like.

Exemplary inorganic solidification agents include phosphate salt (e.g.,alkali metal phosphate), sulfate salt (e.g., magnesium sulfate, sodiumsulfate or sodium bisulfate), acetate salt (e.g., anhydrous sodiumacetate), borates (e.g., sodium borate), silicates (e.g., theprecipitated or fumed forms (e.g., Sipernat 50® available from Degussa),carbonate salt (e.g., calcium carbonate or carbonate hydrate), otherknown hydratable compounds, mixtures thereof, and the like. In anembodiment, the inorganic solidification agent includes organicphosphonate compound and carbonate salt, such as an E-Form composition.

In some embodiments, the compositions include any agent or combinationof agents that provide a requisite degree of solidification and aqueoussolubility. In other embodiments, increasing the concentration of thesolidification agent in the present composition can tend to increase thehardness of the composition. In yet other embodiments, decreasing theconcentration of solidification agent can tend to loosen or soften theconcentrate composition.

The composition may comprise one or more stabilizing agents, forexample, to stabilize peracid and hydrogen peroxide in the compositionand to prevent premature degradation of the constituents.

Suitable stabilizing agents include chelating agents or sequestrants.Suitable agents include organic chelating compounds that sequester metalions in solution, particularly transition metal ions. For example,suitable agents include organic amino- or hydroxy-polyphosphonic acidcomplexing agents (either in acid or soluble salt forms), carboxylicacids (e.g., polymeric polycarboxylate), hydroxycarboxylic acids, oraminocarboxylic acids.

The sequestrant can be or can include phosphonic acid or phosphonatesalt. Suitable phosphonic acids and phosphonate salts include 1-hydroxyethylidene-1,1-diphosphonic acid (HEDP); ethylenediamine tetrakismethylenephosphonic acid (EDTMP); diethylenetriamine pentakismethylenephosphonic acid (DTPMP); cyclohexane-1,2-tetramethylenephosphonic acid; amino[tri(methylene phosphonic acid)]; (ethylenediamine[tetra methylene-phosphonic acid)]; 2-phosphenebutane-1,2,4-tricarboxylic acid; or salts thereof, such as the alkalimetal salts, ammonium salts, or alkyloyl amine salts, such as mono-,di-, or tetra-ethanolamine salts; or mixtures thereof.

Commercially available chelating agents include phosphonates sold underthe trade name DEQUEST® (available from Monsanto Industrial ChemicalsCo., St. Louis, Mo.) including, for example,1-hydroxyethylidene-1,1-diphosphonic acid (DEQUEST® 2010);amino(tri(methylenephosphonic acid)) (DEQUEST® 2000);ethylenediamine[tetra(methylenephosphonic acid)] (DEQUEST® 2041); and2-phosphonobutane-1,2,4-tricarboxylic acid (e.g., BAYHIBIT® AM availablefrom Lanxess GmbH in Leverkusen, Germany).

In some embodiments, the present composition includes stabilizing agentat about 001 to 3 (e.g., 2.5) wt-%, about 0.01 to 2 (e.g., 2.5) wt-%, orabout 0.01 to 1.5 wt-%.

The composition may comprise one or more hydrotropes, also referred toas coupling agents. A hydrotrope can increase the miscibility,solubility or phase stability of organic and inorganic materials inaqueous solution, and can be useful in a composition containing acarboxylic acid or peroxycarboxylic acid, A hydrotrope can alsofacilitate long term physical stability and/or homogeneity of acomposition.

Examples of suitable hydrotropes include nonaqueous liquid carriers orsolvents. Suitable solvents include propylene oxide glycol ether (e.g.,DOWANOL® P Series, available from Dow Chemical, Midland, Mich.) or anethylene oxide based glycol ether. Suitable propylene oxide glycolsinclude a dipropylene glycol n-propyl ether sold under the tradenameDOWANOL by Dow Chemical.

A stabilizing hydrotrope or coupling agent can be present in thecomposition at, for example, about 0.01 to 5 wt-%, about 0.05 to 4 wt-%,or about 0.05 to 3 wt-%.

The pH of the composition may be adjusted to provide optimal sporicidal,antimicrobial, and/or detersive activity. The pH may further be adjustedfor the intended use, such as use with laundry or for cleaning surfacesor objects.

For example, in an embodiment where the composition is used in a laundryapplication and where the amine is added to the laundry first (e.g., aspart I of the composition), the pH of the wash solution may be adjustedto a pH of about 7-12, or to about 9-11. The pH of the solution may beoptimized based on various factors, such as water hardness and othercomponents included in the composition (e.g., part I of thecomposition), or included in a laundry detergent that may be present inthe wash solution at the time the composition is added. If the peracidis added to the wash solution, the pH of the wash solution is loweredand may become neutral or acidic. For example, when the peracid isadded, the pH of the wash solution may be from about 3 to about 9, fromabout 4 to about 8, or from about 4 to about 6, depending on what the pHof the wash solution was prior to adding the peracid. If the pH of thewash solution was elevated prior to adding the peracid, e.g., to about10 to about 11, the addition of the peracid composition (e.g., part IIof the composition) may lower the pH to about 7 to 8.

In an embodiment where the composition is used to clean surfaces, suchas hard surfaces, semi-hard surfaces (e.g., wood or textile-coveredsurfaces), or medical or dental instruments, the pH of the compositionmay be from about 3 to about 10.5, from about 3.5 to about 10, or fromabout 4 to about 9.

Suitable pH modifiers include bases and acids. Examples of bases includealkali metal hydroxides (e.g., sodium hydroxide or potassium hydroxide),amines, carbonates, bicarbonates, and silicates. Examples of acidsinclude organic acids, such as carboxylic acids, and inorganic acids.

The composition can optionally include a buffer. Examples of suitablebuffers include phosphates, carbonates, bicarbonates, and citrates.Exemplary phosphates include anhydrous mono-, di-, or trisodiumphosphate, sodium tripolyphosphate, tetrasodium pyrophosphate andtetrapotassium pyrophosphate. Exemplary carbonates include sodiumcarbonate, potassium carbonate, and sesquicarbonate. Exemplary citratesinclude sodium or potassium citrate.

The composition may optionally include one or more additional functionalingredients including but not limited to dyes or pigments, or perfumes.

Dyes, Pigments, and Perfumes.

Various dyes, pigments, perfumes, and other aesthetic enhancing agentsmay optionally be included in the composition. Dyes may be included toalter the appearance of the composition, as for example, Direct Blue 86(Miles), Fastusol Blue (Mobay Chemical Corp.), Acid Orange 7 (AmericanCyanamid), Basic Violet 10 (Sandoz), Acid Yellow 23 (GAF), Acid Yellow17 (Sigma Chemical), Sap Green (Keyston Analine and Chemical), MetanilYellow (Keystone Analine and Chemical), Acid Blue 9 (Hilton Davis),Sandolan Blue/Acid Blue 182 (Sandoz), Hisol Fast Red (Capitol Color andChemical), Fluorescein (Capitol Color and Chemical), Acid Green 25(Ciba-Geigy), and the like. Fragrances or perfumes that may be includedin the compositions include, for example, terpenoids such ascitronellol, aldehydes such as amyl cinnamaldehyde, a jasmine such asC1S-jasmine or jasmal, SZ-6929 (commercially available from SozioFragrance), vanillin, and the like.

In one embodiment, the composition is provided in a spray bottle andapplied by spraying. For example, the composition may be provided in atwo-chamber spray bottle 1 shown in FIG. 1, where part I is in the firstchamber 11 and part II is in the second chamber 12. Parts I and II getmixed upon application when the composition is sprayed from the spraybottle 1. The spray bottle 1 may include an adjustable mixing assembly14 that allows for the parts to be mixed at a desired ratio. In oneexemplary embodiment, the composition is provided as a kit comprising aspray bottle having two chambers and an adjustable spray assembly influid communication with both chambers, where part I is housed in one ofthe two chambers and comprises about 10 to about 2,000 ppm of etheramine in water; and part II is housed in another of the two chambers andcomprises about 10 to about 2,000 ppm of percarboxylic acid in water.

Methods of Using the Compositions

The disclosed compositions are particularly suitable for use inlaundering textiles and cleaning surfaces, such as hard surfaces,semi-hard surfaces (e.g., wood or textile-covered surfaces), furniture,equipment, and instruments, such as medical and dental instruments.Medical instruments may include, for example, surgical instruments andendoscopic instruments. The composition can be formulated with thedesired end-use in mind.

The composition can be used at room temperature or at higher or lowertemperatures, such as at about 10° C. to about 99° C., about 15° C. toabout 90° C., about 20° C. to about 80° C., about 25° C. to about 70° F.In some examples the composition is used at room temperature, e.g., atabout 18° C. to about 30° C., or at about 18° C. to about 26° C. In someother examples, the composition is used at an elevated temperature, suchas about 40° C., about 50° C., or about 60° C. The effectiveness of thecomposition may be increased at elevated temperatures.

In laundry applications, the composition can be applied to the washwater directly, either by dosing the components separately(simultaneously or consecutively), or by dosing a mixture of components.The composition can be dosed as a concentrate or as a diluteduse-solution. The composition may be dosed into the wash solution beforeor after applying the wash solution onto the textiles, or can be applieddirectly onto the textiles. The composition may be used as apre-treatment or as a post-treatment (e.g., as a rinse). The compositioncan also be formulated as a detergent composition or be usedsimultaneously with a detergent composition.

According to embodiments, the dosage sequence of the ether aminecomponent and the peracid component can be varied, in part, based on theconcentration of the components. The term “dosage” is used here to referto the final concentration of the components in the use solution (e.g.,the wash solution). In some embodiments, when the dosage of the etheramine is about 2,000 ppm or less (e.g., between about 10 ppm and 2,000ppm), and the dosage of the peracid is about 2,000 ppm or less (e.g.,between about 10 ppm and 2,000 ppm), the components can be dosedsimultaneously. In certain other embodiments, when the dosage of theether amine is more than about 2,000 ppm (e.g., between about2,000-10,000 ppm), the components are dosed sequentially. For example,in some embodiments, the ether amine component is dosed into a firstwash solution first and the first wash solution is applied to thetextiles; the first wash solution is drained, and the peracidcomposition is applied to a second wash solution that is applied to thetextiles. After the second wash solution is drained, the textiles can berinsed or subjected to another wash cycle (optionally with a detergentcomposition). It will be appreciated by those skilled in the art thatembodiments of the methods disclosed here also encompass morecomplicated dosing sequences. For example, more sequential steps can beadded to the method, dosing each of the components more than once,optionally at different concentrations, varying the order of dosing.

According to some embodiments, the composition can be used to treatsurfaces, such as food handling surfaces (e.g., countertops, foodhandling equipment and utensils), general premise surfaces (e.g.,floors, walls, ceilings, exterior of furniture, etc.), or equipmentsurfaces (e.g., medical equipment, manufacturing equipment, processingequipment, etc.). The composition can be applied to the surface to betreated by any suitable method, such as spraying, pouring, dripping,wiping, or mopping, etc. The composition can be provided as, forexample, a ready-to-use spray or cleaning wipe. In one embodiment, thecomposition is applied to the surface as a mixture comprising etheramine and peracid. In another embodiment, the composition is a two partcomposition, where part I is applied to the surface first, and part IIsecond. A two-part composition can also be used by mixing parts I and IItogether prior to application to a surface or to an object.

EXAMPLES

Various compositions were prepared and tested for removal of microbialspores from cotton fabric and from a glass surface. The experimentalconditions and results are detailed in the Examples below.

Example 1

Aqueous solutions of ether amine (Part I) and peracid (Part II) wereprepared. Ether amine (octyl/decyloxypropyl-1,3-diaminopropane) solution(Part I) was prepared in deionized water and the pH was adjust to 9.0using glycolic acid. TOMAMINE DA1214 was used as the ether amine.TOMAMINE DA1214 contains about 50-60% by weight of 1,3-Propanediamine,N-[3-(octylocy)propyl] and about 35-40% by weight of 1,3-Propanediamine,N-[3-(decylocy)propyl], and is available from Air Products andChemicals, Inc., in Allentown, Pa. Peracid (peracetic acid) solution(Part II) was prepared from TSUNAMI® 100 (15 peracetic acid), availablefrom Ecolab Inc., in St Paul, Minn.

Cotton fabric swatches (5 mm×5 mm) were inoculated with C. Diff. AATCC43598 at 35° C. for 48 hours. After inoculation, the swatches weretreated with a first solution comprising part I of the composition at50° C. for a first exposure time; removed from the first solution withsterile forceps and immediately transferred into a second solutioncomprising part II of the composition for a second exposure time. Incomparative treatments, the solutions included only water. Aftertreatment, the number of surviving spores was evaluated, and the logreduction of spores was compared to the comparative treatment (wateronly).

In Example 1, the first exposure time was 10 minutes (Part I) and thesecond exposure time was 5 minutes (Part II).

Three experiments were conducted. The results are shown in TABLES 3A-3Cbelow.

TABLE 3A Fabric Swatches, Consecutive Treatment Part I Part II etheramine peracid Average Average Log (ppm) (ppm) Survivors Log Reduction 00 2.4 × 10⁶ 6.38 — 5000 300 1.4 × 10⁴ 4.15 2.23 0 300 2.3 × 10⁵ 5.361.02 5000 500 <10 <1.0 5.38 0 500 1.7 × 10³ 3.23 3.15 5000 0 1.3 × 10⁶6.11 0.27

TABLE 3B Fabric Swatches, Consecutive Treatment Part I Part II etheramine peracid Average Average Log (ppm) (ppm) Survivors Log Reduction 00 1.3 × 10⁶ 6.11 — 5000 300 3.1 × 10⁴ 4.49 1.62 2000 300 3.0 × 10¹ 1.484.63 500 300 5.5 × 10¹ 1.74 4.37 100 300 4.0 × 10¹ 1.60 4.51

TABLE 3C Fabric Swatches, Consecutive Treatment Part I Part II etheramine peracid Average Average Log (ppm) (ppm) Survivors Log Reduction 00 5.4 × 10⁵ 5.73 — 100 300 2.0 × 10¹ 1.30 4.43 75 300 2.5 × 10¹ 1.404.33 50 300 2.6 × 10¹ 2.41 3.32 25 300 1.2 × 10² 2.08 3.65 0 300 1.1 ×10⁵ 5.04 0.69

It was noted that neither one of the treatments (ether amine or peracid)alone resulted in a significant reduction in spores. A concentration of5000 ppm of ether amine achieved a log reduction of 0.27, and 300 ppm ofperacid a log reduction of 1.02 (TABLE 3A) and 0.69 (TABLE 3C); 500 ppmof peracid achieved a log reduction of 3.15. It was further noted thatapplication of part I and part II separately resulted in a synergisticeffect, achieving significant log reductions. However, a highconcentration (5000 ppm) of ether amine with 300 ppm of peracid resultedin a lower log reduction (2.23 in TABLE 3A and 1.62 in TABLE 3B), thanlower concentrations. The synergistic effect was strongest atconcentrations of less than 5000 ppm of ether amine.

Without wishing to be bound by theory, it was hypothesized thatapplication of a high concentration (5000 ppm) of ether amine leftresidual ether amine on the fabric swatches, and when the swatches weremoved into the second solution, the residual ether amineantagonistically reacted with the peracid.

Example 2

The treatment described above for Example 1 was applied to glass squares(5 mm×5 mm) in a first part of the experiment, where the first exposuretime was 10 minutes (part I) and the second exposure time was 5 minutes(part II). In a second part of the experiment, the ether amine andperacid were mixed together prior to treatment, and the exposure timewas 15 minutes. Results of the first part of the experiment are shown inTABLE 4A, and of the second part of the experiment in TABLE 4B.

TABLE 4A Glass Surface, Consecutive Treatment Part I Part II ether amineperacid Average Average Log (ppm) (ppm) Survivors Log Reduction 0 0 4.6× 10⁶ 6.66 — 5000 300 <10 <1.00 >5.66 0 300 2.0 × 10⁵ 5.30 1.36 5000 500<10 <1.00 >5.66 0 500 2.4 × 10³ 3.38 3.28

TABLE 4B Glass Surface, Simultaneous Treatment Part I Part II etheramine peracid Average Average Log (ppm) (ppm) Survivors Log Reduction 00 8.8 × 10⁵ 6.66 — 4500 300 2.6 × 10⁵ 5.41 0.53 4500 500 2.2 × 10⁵ 5.340.60

Consecutive treatment with part I and part II resulted in elimination ofvirtually all spores from the glass squares. In contrast, when etheramine and peracid were mixed together, little reduction of spores wasachieved.

Without wishing to be bound by theory, it was hypothesized that thatether amine and peracid, when mixed together, act antagonisticallyagainst each other, thus preventing from acting against the spores.

Example 3

The treatment described in Example 2 was repeated at room temperature(“RT,” approximately 23° C.). Part I was prepared with ether amineDA-1214 and Part II with peroxyacetic acid. The exposure times were 10min for Part I and 5 min for Part II. The results are shown in Table 5below.

TABLE 5 Glass surface, room temperature. Part I Part II ether amineperacid Average Average Log (ppm) (ppm) Survivors Log Reduction 0 0 63 ×10⁵ 6.8 — 0 1000 >300 × 10³  >5.48 <1.32 100 1000 77 × 10¹ 2.89 3.91

It was observed that adding an ether amine treatment to the peracidimproved the log reduction even at room temperature.

Example 4

Consecutive and simultaneous treatment with low concentration (100 ppm)of ether amine and peracetic acid was tested on fabric squares. Thefabric squares were treated as in Example 1 with treatment times of 10min (part I) and 5 minutes (part II), except with the simultaneoustreatment, where ether amine and peracid were mixed prior to treatmentand the exposure time was 5 minutes.

Results are shown in Table 6 below.

TABLE 6 Fabric swatches, Consecutive vs. Simultaneous Treatment Part IPart II ether amine peracid Log (ppm) (ppm) Reduction Consecutive 0 0 —Consecutive 0 300 0.85 Consecutive 100 300 3.45 Simultaneous 100 3003.81

The log reductions of the consecutive and simultaneous treatments werevery similar. It was concluded that as long as the concentration ofether amine is kept relatively low, the components (part I and part II)can be mixed together during treatment without significant loss ofefficiency.

Example 5

Various ether amines were tested for their efficiency in eradicatingbacterial spores from fabric swatches. The fabric swatches were treatedaccording to ASTM protocol for evaluating laundry sanitizers anddisinfectants (ASTM E2274-09). The ASTM protocol provides more realisticconditions for laundering textiles, where the tested textiles areimbedded within a bundle of fabrics to mimic the ability of thecomposition to penetrate the fabric with less exposure to the washsolution.

Three different ether amine solutions were tested: DA-1214(octyl/decyloxypropyl-1,3-diaminopropane), DA-1618(dodecyl/tetradecyloxypropyl-1,3-diaminopropane), and PA-14(isodecyloxypropyl amine). Part I and Part II were both added togetherat the start of the experiment for a combined exposure time of 10minutes. The solutions were made into deionized water as described inExample 1, with the pH adjusted to 9.0 by glycolic acid. However, PA-14was already neutralized to pH 7 with sodium acetate. The log reductionof spores was measured in the wash solution and on the fabric swatch.The reduction of spores was compared to number of spores in the baselinetreatment (water only). Results of the testing are shown in TABLE 7below.

TABLE 7 Fabric Swatches (ASTM protocol), Simultaneous treatment Part IPart II Wash Solution Fabric Swatch Part I ether amine peracid Log LogEther Amine (ppm) (ppm) Reduction Reduction DA-1214 100 0 0.01 0.00DA-1618 100 0 0.12 0.02 PA-14  100 0 0.17 0.07 DA-1214 100 200 5.63*5.34 DA-1618 100 200 5.63* 5.97* PA-14  100 200 5.63* 4.63 — 0 200 5.332.65 *Killed all spores present

It was found that the amines alone had virtually no impact of spores ineither the wash solution or on the fabric swatch, while the peracidalone was effective in eliminating spores in the wash solution, but lessso on the fabric swatch. Consecutive treatments with each of the etheramines and peracid eliminated all of the spores in the wash solution andwere also effective against spores on the fabric swatches. It was foundthat of the ether amines tested, DA-1618 was the most effective againstspores on fabric swatches.

Example 6

Treatment of fabric swatches was tested in pH-adjusted hard water. Thewash solution contained 500 ppm synthetic hard water, and the pH wasadjusted to 10.5 with NaOH prior to peracid addition. After the additionof the peracid, pH of the wash solution was between 7-8. DA-1214 wasused as the ether amine and peracetic acid as the peracid.

The log reduction of spores was measured in the wash solution and on thefabric swatch. The reduction of spores was compared to number of sporesin the baseline treatment (water only). The combined treatment time was10 minutes. Results of the testing are shown in TABLE 8 below.

TABLE 8 Fabric Swatches (ASTM E2274), Simultaneous Treatment, Hard WaterPart I Part II Wash Solution Fabric Swatch ether amine peracid Log Log(ppm) (ppm) Reduction Reduction 0 200 5.30 3.01 100 200 6.15* 6.30**Killed all spores present

It was found that the treatment with ether amine and peracid killed allof the spores present in the wash solution and on the fabric swatch. Itwas concluded that the effectiveness of the consecutive treatment withether amine and peracid was not reduced by the alkaline hard water.

Example 7

The use of different peracids was tested. Fabric swatches were treatedusing the ASTM test described in Example 5. Part I was prepared with 100ppm ether amine (DA-1618). Part II was prepared with 200 ppm ofperoxyacetic acid (“POAA”) or peroxyoctanoic acid (“POOA”). When bothPart I and Part II were used, the chemicals were added simultaneously.The exposure time was 10 min at 50° C. The results are shown in TABLE 9below.

TABLE 9 Peracid comparison. Part I Part II Wash Solution Ether aminePeracid Log Carrier log 100 ppm 200 ppm Reduction reduction — POAA 4.401.78 DA-1618 POAA 6.00* 5.78* — POOA 6.00* 5.35 DA-1618 POOA 6.00* 1.70

It was observed that adding ether amine to peroxyacetic acid resulted ina significant increase in the kill. Peroxyoctanoic acid alone was nearlyas effective as peroxyacetic acid and ether amine together. However,adding ether amine to the peroxyoctanoic acid reduced the kill. It wasnoted that peroxyoctanoic acid and ether amine are both veryhydrophobic, and thus have an affinity to each other. It was thereforehypothesized that when the two chemicals were added simultaneously insolution they agglomerated together and caused a reduction in the kill.

While certain embodiments of the invention have been described, otherembodiments may exist. While the specification includes a detaileddescription, the invention's scope is indicated by the following claims.Furthermore, while the specification has been described in languagespecific to structural features and/or methodological acts, the claimsare not limited to the features or acts described above. Rather, thespecific features and acts described above are disclosed as illustrativeaspects and embodiments of the invention. Various other aspects,embodiments, modifications, and equivalents thereof which, after readingthe description herein, may suggest themselves to one of ordinary skillin the art without departing from the spirit of the present invention orthe scope of the claimed subject matter.

What is claimed is:
 1. A method for eliminating bacterial spores on anarticle suspected of contamination with bacterial spores, the methodcomprising: preparing a first use solution by mixing about 10 to about2,000 ppm of ether amine in water and a second use solution by mixingabout 10 to about 2,000 ppm of percarboxylic acid in water; applying thefirst use solution to the article; and applying the second use solutionto the article.
 2. The method of claim 1, wherein the ether aminecomprises one or more ether amines having 1-22 carbon atoms.
 3. Themethod of claim 1, wherein the ether amine comprises one or more etheramines having 10-18 carbon atoms.
 4. The method of claim 1, wherein thefirst use solution comprises 25-1,500 ppm ether amine.
 5. The method ofclaim 1, wherein the first use solution comprises 25-1,000 ppm etheramine.
 6. The method of claim 1, wherein the first use solutioncomprises 50-500 ppm ether amine.
 7. The method of claim 1, wherein thepercarboxylic acid comprises one or more percarboxylic acids having 2-12carbon atoms.
 8. The method of claim 1, wherein the second use solutioncomprises 10-1,500 ppm percarboxylic acid.
 9. The method of claim 1,wherein the second use solution comprises 50-1,000 ppm percarboxylicacid.
 10. The method of claim 1, wherein the second use solutioncomprises 50-500 ppm percarboxylic acid.
 11. The method of claim 1,wherein the method is capable of at least 2-log reduction of bacterialspores selected from C. diff, C. botulinum, C. sporogenes, B. cereus,and B. subtilis.
 12. The method of claim 1, wherein the method iscapable of at least 3-log reduction of bacterial spores selected from C.diff, C. botulinum, C. sporogenes, B. cereus, and B. subtilis.
 13. Themethod of claim 1, wherein the method is capable of at least 4-logreduction of bacterial spores selected from C. diff, C. botulinum, C.sporogenes, B. cereus, and B. subtilis.
 14. The method of claim 1,wherein the article comprises a textile or a hard surface.
 15. Themethod of claim 1, wherein at least one of the first use solution andsecond use solution further comprises one or more surfactants.
 16. Themethod of claim 1, wherein at least one of the first use solution andthe second use solution further comprises one or more pH modifiers. 17.The method of claim 1, wherein the first use solution and the second usesolution are applied simultaneously to the article.
 18. The method ofclaim 1, wherein the first use solution and the second use solution areapplied consecutively to the article.
 19. The method of claim 1, whereinthe first use solution and the second use solution are appliedcumulatively to the article.
 20. The method of claim 1, wherein one ofthe first use solution and the second use solution is a laundry booster.21. The method of claim 1, wherein one of the first use solution and thesecond use solution is applied to a hard surface of the article.
 22. Themethod of claim 21, wherein one of the first use solution and the seconduse solution is applied to the article by spraying, pouring, wiping, ormopping.
 23. A method for eliminating bacterial spores, the methodcomprising: preparing a first use solution by mixing about 10 to about3,000 ppm of ether amine in water; preparing a second use solution bymixing about 10 to about 3,000 ppm of percarboxylic acid in water;applying the first use solution to an article suspected of contaminationwith bacterial spores; applying the second use solution the articlesuspected of contamination with bacterial spores.
 24. The method ofclaim 23, wherein the first use solution comprises 25-2,000 ppm etheramine.
 25. The method of claim 23, wherein the first use solutioncomprises 50-1,500 ppm ether amine.
 26. The method of claim 23, whereinthe first use solution comprises 50-1,000 ppm ether amine.
 27. Themethod of claim 23, wherein the second use solution comprises 10-2,000ppm percarboxylic acid.
 28. The method of claim 23, wherein the seconduse solution comprises 50-1,500 ppm percarboxylic acid.
 29. The methodof claim 23, wherein the second use solution comprises 50-1,000 ppmpercarboxylic acid.
 30. The method of claim 23, wherein applying thefirst use solution comprises immersing the article in the first usesolution, and applying the second use solution comprises immersing thearticle in the second use solution, the method further comprisingdraining the first use solution before applying the second use solution.31. The method of claim 23, wherein the first use solution and thesecond use solution are applied simultaneously to the article.
 32. Themethod of claim 23, wherein the first use solution and the second usesolution are applied cumulatively to the article.